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Cation-Mutation Design of Quaternary Nitride Semiconductors Lattice-Matched to GaN

Cai, Zeng-Hua and Narang, Prineha and Atwater, Harry A. and Chen, Shiyou and Duan, Chun-Gang and Zhu, Zi-Qiang and Chu, Jun-Hao (2015) Cation-Mutation Design of Quaternary Nitride Semiconductors Lattice-Matched to GaN. Chemistry of Materials, 27 (22). pp. 7757-7764. ISSN 0897-4756. doi:10.1021/acs.chemmater.5b03536.

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The search for new direct bandgap, earth-abundant semiconductors for efficient, high-quality optoelectronic devices, as well as photovoltaic and photocatalytic energy conversion has attracted considerable interest. One methodology for the search is to study ternary and multiternary semiconductors with more elements and more flexible properties. Cation mutation such as binary → ternary → quaternary for ZnS → CuGaS_2 → Cu_2ZnSnS_4 and ZnO → LiGaO_2 → Li_2ZnGeO_4 led to a series of new quaternary chalcogenide and oxide semiconductors with wide applications. Similarly, starting with GaN, ternary nitrides such as ZnSnN_2 and ZnGeN_2 have been designed and synthesized recently. However, quaternary nitride semiconductors have never been reported either theoretically or experimentally. Through a combination of the Materials Genome database with the first-principles calculations, we designed a series of quaternary nitride compounds I–III–Ge_2N_4 (I = Cu, Ag, Li, Na, K; III = Al, Ga, In) following the GaN → ZnGeN_2 → I–III–Ge_2N_4 mutation. Akin to Li_2ZnGeO_4, these quaternary nitrides crystallize in a wurtzite-derived structure as their ground state. The thermodynamic stability analysis shows that while most of them are not stable with respect to phase separation, there are two key exceptions (i.e., LiAlGe_2N_4 and LiGaGe_2N_4), which are stable and can be synthesized without any secondary phases. Interestingly, they are both lattice-matched to GaN and ZnO, and their band gaps are direct and larger than that of GaN, 4.36 and 3.74 eV, respectively. They have valence band edges as low as ZnO and conduction band edges as high as GaN, thereby combining the best of GaN and ZnO in a single material. We predict that flexible and efficient band structure engineering can be achieved through forming GaN/LiAlGe_2N_4/LiGaGe_2N_4 heterostructures, which have tremendous potential for ultraviolet optoelectronics.

Item Type:Article
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URLURL TypeDescription Information
Narang, Prineha0000-0003-3956-4594
Atwater, Harry A.0000-0001-9435-0201
Additional Information:© 2015 American Chemical Society. Received: September 9, 2015. Revised: October 31, 2015. Published: November 2, 2015. We thank Prof. Jiang Tang for the helpful discussion about the viable synthesis strategy. The work was supported by the National Natural Science Foundation of China (grant no. 91233121, 61125403), Shanghai Rising-Star Program (grant no. 14QA1401500), Special Funds for Major State Basic Research (grant no. 2012CB921401, 2014CB921104), PCSIRT and the computer center of ECNU. P.N. is supported by the National Science Foundation and the Resnick Sustainability Institute at Caltech. The authors declare no competing financial interest.
Group:Resnick Sustainability Institute
Funding AgencyGrant Number
National Natural Science Foundation of China91233121
National Natural Science Foundation of China61125403
Shanghai Rising-Star Program14QA1401500
Special Funds for Major State Basic Research2012CB921401
Special Funds for Major State Basic Research2014CB921104
Program for Changjiang Scholars and Innovative Research Team in University (PCSIRT)UNSPECIFIED
Resnick Sustainability InstituteUNSPECIFIED
Issue or Number:22
Record Number:CaltechAUTHORS:20160104-163003841
Persistent URL:
Official Citation:Cation-Mutation Design of Quaternary Nitride Semiconductors Lattice-Matched to GaN Zeng-Hua Cai, Prineha Narang, Harry A. Atwater, Shiyou Chen, Chun-Gang Duan, Zi-Qiang Zhu, and Jun-Hao Chu Chemistry of Materials 2015 27 (22), 7757-7764 DOI: 10.1021/acs.chemmater.5b03536
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:63355
Deposited By: George Porter
Deposited On:05 Jan 2016 19:22
Last Modified:10 Nov 2021 23:15

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